CA1214675A - Colour-photographic recording material - Google Patents
Colour-photographic recording materialInfo
- Publication number
- CA1214675A CA1214675A CA000417792A CA417792A CA1214675A CA 1214675 A CA1214675 A CA 1214675A CA 000417792 A CA000417792 A CA 000417792A CA 417792 A CA417792 A CA 417792A CA 1214675 A CA1214675 A CA 1214675A
- Authority
- CA
- Canada
- Prior art keywords
- group
- alkyl
- hydrogen
- formula
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 title claims abstract description 35
- -1 silver halide Chemical class 0.000 claims abstract description 90
- 239000004611 light stabiliser Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000011229 interlayer Substances 0.000 claims abstract description 4
- 239000011241 protective layer Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 58
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 49
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 48
- 150000002431 hydrogen Chemical group 0.000 claims description 37
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 16
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000005394 methallyl group Chemical group 0.000 claims description 7
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 4
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 101100173726 Arabidopsis thaliana OR23 gene Proteins 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- LFMFPKKYRXFHHZ-UHFFFAOYSA-N R24 Chemical compound C1=C(Cl)C(C)=CC=C1NC1=NC(N)=C(C=CC=C2)C2=N1 LFMFPKKYRXFHHZ-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000005628 tolylene group Chemical group 0.000 claims description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000006839 xylylene group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 2
- SLYRGJDSFOCAAI-UHFFFAOYSA-N 1,3-thiazolidin-2-one Chemical compound O=C1NCCS1 SLYRGJDSFOCAAI-UHFFFAOYSA-N 0.000 claims 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims 1
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 239000001828 Gelatine Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101100448208 Human herpesvirus 6B (strain Z29) U69 gene Proteins 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- KWZKVJAJEQXPED-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-cyanoacetate Chemical compound CC1(C)CC(OC(=O)CC#N)CC(C)(C)N1 KWZKVJAJEQXPED-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006227 2-n-butoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- YSMODUONRAFBET-UHFFFAOYSA-N 5-hydroxylysine Chemical group NCC(O)CCC(N)C(O)=O YSMODUONRAFBET-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 235000010650 Hyssopus officinalis Nutrition 0.000 description 1
- 240000001812 Hyssopus officinalis Species 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/96—Sulfur atom
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/162—Protective or antiabrasion layer
Abstract
Colour-photographic recording material Abstract A colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an interlayer and/or a protective layer, contains at least one polyalkylpiperidine compound of the formula I
(I) as a light stabiliser.
Colour images obtained by imagewise exposure and development of this colour-photographic recording material display good stability to the action of visible and ultra-violet light.
With respect to the definitions of the substituents and symbols in formula I, reference is made to claim 1.
(I) as a light stabiliser.
Colour images obtained by imagewise exposure and development of this colour-photographic recording material display good stability to the action of visible and ultra-violet light.
With respect to the definitions of the substituents and symbols in formula I, reference is made to claim 1.
Description
12~675 3-1371L/S/+
Colour-photographic recording material The present invention relates to a colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer and/or in at least one of the conventional auxiliary layers, contains at least one polyalkylpiperidine ligh~-stabiliser.
In European Patent Application 11,051, a colour-photographic recording material has already been described, which contains a polyalkylpiperidine light-stabiliser in order to improve the lightfastness of the colour images obtained with this material and to suppress undesired fogging.
It has now been found that, surprisingly, an even better light-stabilising effect can be achieved when the compounds of the formula I, described below, are incorporated into the colour-photo-graphic recording material.
e present application therefore relates to a colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an inter-layer and/or a protective layer, contains at least one polyalkylpipcridi~ compound as a light stabiliser, wherein the polyalkylpiperidine compound is of the formula I
5\._. ~ 3 H0--~ 4. ~ 2 1 (I) -~ >\(A)m-(C-Y)n- \ ~N R2 C~3 CH2R
~#~
in which Rl and R3 independently of one another are hydrogen or methyl, R2 is hydroxyl, Cl-C12-alkyl, C3-C12-alkenyl, C3-C4-alkynyl,
Colour-photographic recording material The present invention relates to a colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer and/or in at least one of the conventional auxiliary layers, contains at least one polyalkylpiperidine ligh~-stabiliser.
In European Patent Application 11,051, a colour-photographic recording material has already been described, which contains a polyalkylpiperidine light-stabiliser in order to improve the lightfastness of the colour images obtained with this material and to suppress undesired fogging.
It has now been found that, surprisingly, an even better light-stabilising effect can be achieved when the compounds of the formula I, described below, are incorporated into the colour-photo-graphic recording material.
e present application therefore relates to a colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an inter-layer and/or a protective layer, contains at least one polyalkylpipcridi~ compound as a light stabiliser, wherein the polyalkylpiperidine compound is of the formula I
5\._. ~ 3 H0--~ 4. ~ 2 1 (I) -~ >\(A)m-(C-Y)n- \ ~N R2 C~3 CH2R
~#~
in which Rl and R3 independently of one another are hydrogen or methyl, R2 is hydroxyl, Cl-C12-alkyl, C3-C12-alkenyl, C3-C4-alkynyl,
2-hydroxyethyl, C2-Cll-alkoxyalkyl, C7-Cl4-aralkyl or a group of the formula -(CH2)p-CH(R6)-Xl or -CH(R6)-X2, in which p is one of the numbers l, 2 or 3, Xl is halogen, cyano, -OR7, -OC(O)R7, -OC(O) N(R7)(R8), -C(O)OR7 or -C(O)N(R7)(R~), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen. methyl or yhenyl, R7 being hydrogen, Cl-Cl2-alkyl, C2-Cl2-alkenyl, C3-C12-cycloalkyl, phenyl, C7-Cl4-alkaryl or C7-Cl4-aralkyl and R8 being hydrogen or Cl-C4-alkyl, or R7 and R8, together with the nitrogen atom to which they are bonded, forming a 5-membered or 6-membered heterocyclic ring, or R2 is a group of the formula II
L-CO- (II) in which L is hydrogen, Cl-Cl2-alkyl, C2-Cl2-alkenyl, C3-C4-alkynyl, C3-C12-cycloalkyl, C7-C14-alkaryl, C7-C14-aralkyl, chloro-methyl, unsubstiLuted phenyl, phenyl which is substituted by two Cl-C4-alkyls and one hydroxyl, or a group -ORg, in which Rg is Cl-C12-alkyl, cyclohexyl, C2-C12-alkenyl, benzyl or phenyl, or L is a group of the formula III
R3 ~ 4 ( )m \ / (III) \R5 or R2 is a group of the formula IV
C ~ lO (IV) o 1 1 in which Rlo and Rll independently of one another are Cl-Cl2-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-Cl4-aralkyl and Rll additionally can also be hydrogen, or R2 is a group of the formula V
~4675 ~H
R 4\ ~ \ / 5 -CH2-CH(R12)-SY-C)-(A') (V) in which A' is methylene or a group -CH2-CH(R13)- and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenyl, or R2 is a group of the formula VI
1 2\./. 3 0 R4\ ~!, /R5 -B-~ (y-c)n-(A) il (VI) ~ R3 in which B is a group CrH2r, in which r is a number from 2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, phenylene, xylylene, bitolylene, C5-C12-cycloalkylene o~ a group -CONH-Bl-NHCO-, in which Bl is a group CrH2r, phenylene, nahpthylene, tolylene or a group of the formulae CH3 \ /. , ~ -C~ -- or -.\ \--C--/ \.
CH3 R R' R" R R' R"
in which R' is hydrogen, methyl or ethyl, R" is hydrogen or methyl and r is a defined above, or R2 is one of the groups -S(O) R14 or -OR15, in which z is the number 1 or 2, Rl4 i9 Cl-C12-alkyl, C7-C14-alkaryl or phenyl and Rl5 is Cl-C12-alkyl, C3 C12 a Y ' 7 14 aralkyl or a group of the formula L'-CO-, in which L' is as defined above for L, R4 and R5 independently of one another are Cl-C12-alkyl, C3-C12-cycloalkyl, C7-C14-aralkyl, C7-C14 alkaryl or phenyl and R4 can additionally also be hydrogen or a group of the formula Ia :1214f~75 OH
~ ~ (A) (Rc-y)- .' ~ -R (la) CH~ CH2Rl in which Rl, R2, R3, R5, A, Y, m and n are as defined and M is a direct bond, -8-~ s s s ~ s -CH -S-CH --CH2-O-CH2-, -O- and -N(D3)-, and Dl and D2 independently of one another are hydrogen, Cl-C18-alkyl, alkyl interrupted by 1 to 3 -S- or phenyl, or Dl and D2, together with the C atom linking the~, form a 5-membered or 6-membered aliphatic ring and D3 is hydrogen, Cl-C18-alkyl or phenyl, Y i9 -O-, n and m independently of one another are zero or 1, and A is methylene or a group -CH2-CH(R20)-or -CH2-C(E)(G)-, in which R20 is hydrogen, methyl, ethyl, phenoxy-methyl or phenyl, E is cyano or a group -C(O)OR21, -C(O)R22, -S02R22, -P(O)(OR23)2, -C(O)NR24R25 or -CHO, in which R21 is 1 4 Y ~ 22 ig ~1 C12-alkyl, C7-C14-alkaryl or phenyl 9 R
i9 Cl-C18-alkyl, phenyl or allyl, and R24 and R25 independently of one another are hydrogen, Cl-C18-alkyl or phenyl, and G is hydrogen, Cl-C18-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-cl8-alkylcycloalkvl~ C6-C14-cycloalkylalkyl. C7-C14-aralkyl, C7-Clg-alkyl-aralkyl, phenyl, or Cl-C18-alkyl which is substituted by phenoxy, C7-C10-alkylphenoxy, benzyloxy, cyclohexyloxy, cyano, -COOR26, -OCOR27 or -P(O)(OR28)2, R26 being Cl-C18-alkyl, C3-C12-cycloalkyl or a group of the formula VII
~;~1467~
1\,~3./ 2 1 _. (VII) C~3 CH2R
R27 being Cl-C18-alkyl, c3-C12-cycloalkYl, phenyl, C7-C14~aralkYl or a group of the formula III and R28 being Cl-C18-alkyl, allyl or phenyl, or G is C2-C18-alkyl interrupted by -O-, -S-, -SO- or -SO2-, a group of the formula VII or a group of the formula 2 \ ~--OH
=.
~ 30 in which R29 and R30 independently of one another are Cl-C4-alkyl and R30 additionally can also be hydrogen, or, if E is a group -C(O)R22, G and R22 together are trimethylene or tetramethylene.
Cl-C12-Alkyl substituents which may be present can be branched or unbranched alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-pentyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-nonyl, decyl or dodecyl. Cl-C4-Alkyl is preferred. cl-Cl~-AlkYl radicalg R16 and R23 can additionally be, for example, tridecyl, tetradecyl9 hexadecyl or octadecyl.
Cl-C4-Alkyl substituents which may be present are methyl,ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or tert.-butyl.
C3-C12-Alkenyl substituents which may be present are, for example, allyl, methallyl, 2-butenyl, Z-hexenyl, 2-octenyl, 4-octenyl, 2-decenyl or 2-dodecenyl. Allyl is preferred. C2-C12-Alkenyl substituents can additionally also be vinyl. In this case, vinyl and allyl are preferred.
C
~, ~4~;7X
C3-C4-Alkynyl radicals R2, G and L are, for example, propargyl, n-but-l-ynyl or n-but-2-ynyl.
Propargyl is preferred.
C3-Cll-Alkoxyalkyl radicals R2 are, for exa~ple, ethoxymethyl, 2--me-thoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 2-n-butoxypropyl, 2-n-octoxyethyl, 3-n-octoxypropyl or 6-n-butoxyhexyl. Additionally, a C2-alkoxyalkyl radical R2~can also be methoxymethyl.
Halogens Xl and X2 are, for example, bromine, iodine and in particular chlorine.
C3-C12-Cycloalkyl substituents which may be present are, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, -methyl-cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, or cyclododecyl.
Cyclohexyl is preferred.
C7-C14-Alkaryl substituents which may be present are, for example, phenyl substituted by Cl-C4-alkyl, such as p-tolyl, 2,4-dimethyl-phenyl, 2,6-dimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 4-tert.-butylphenyl, 2,4-di-tert.-butylphenyl or 2,6-di-tert.-butylphenyl. 2,4-Di-tert.-butylphenyl and 2,4-dimethylphenyl are preferred.
5-Membered or 6-membered heterocyclic rings, fonmod by R7 and R8 together with the nitrogen atom to which they are bonded, are, for example, pyrrolidine, oxazolidine, piperidine or morpholine radicals.
C7-C14-Aralkyl substituents which may be present are, for example, benzyl, p-methylbenæyl, p-tert.-butylbenzyl, l-phenylethyl, dimethylbenzyl or 2-phenylethyl.
~2~467~
In -C H2 ~ groups B or Bl in which r is a number between 1 and 12, r preferably is a number between 2 and 8. Examples are methylene, ethylene, trimethylene, tetramethylene, hexamethylene, ortanethylene, nonamethylene, 2,2,4-trimethylhexamethylene, decamethylene and dodecamethylene.
C4-C8-Alkenylene radicals B are, for example, but-2-en-1,4--ylene.
C4-C8-Alkynylene radicals B are, for example, but-2-yn-1,4-ylene.
C5-C12-Cycloalkylene radicals B are, for example, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene or cyclododecylene.
Cyclohexylene is preferred.
Cl-C12-Alkyl radicals G, substituted by phenoxy, benzyloxy, cyclo-hexyloxy or cyano, can, for example, be one of the following radicals: 2-phenoxyethyl, 2-ben~yloxyethyl, cyclohexyloxymethyl, 2-cyanoethyl, cyanomethyl or 3-cyanopropyl.
C6-C18-Alkylcycloalkyl radicals G are, for example, methylcyclo-hexyl, ethylcyclohexyl, butylcyclohexyl, tert.-butylcyclohexyl, dodecylcyclohexyl, ethylcyclopentyl or butylcyclopentyl and C6-Cl4-cycloalkylalkyl radicals G are, for example, cyclohexylme-thyl, cyclohexylethyl, cyclohexylbutyl, cyclohexylhexyl, cyclo-hexyloctyl, cyclopentyipropyl or cyclopenthylhexyl.
Cl-C18-Alkyl radicals G, substituted by C7-C10-alkylphenoxy, can be, for example, p-methylphenoxymethyl, p-methylphenoxyethyl, p-methylphenoxypropyl, p-tert.-butylphenoxymethyl, p-tert.-butylphenoxyethyl, 2,4-dimethylphenoxymethyl, 2,4-dimethylphenoxy-ethyl, 2,4-di-tert.-butylphenoxyethyl, 2,6-di-tert.-butylphenoxy-methyl or 2,4,6-trimethylphenoxyethyl.
~;~14ti7~
C2-C12-Alkyl radicals G interrupted by -O-, -S-, -SO- or -SO2-are, for example, one of the following radicals: methoxymethyl, 2-butoxyethyl, 2-octyloxyethyl, isopropoxymethyl, 3-butylthiopropyl, 2-decylthioethyl, 2-(isohexylsulfinyl)-ethyl, 2-(butylsulfonyl)-ethyl or 2-(ethylsulfonyl)-propyl.
Those colour-photographic recording materials are preferred which contain, as the light stabiliser, at least one compound of the formula X
4\._. 1\.~3./ 2 1 \ / ( )m ( )n \ ~ 2 (X) R5 C~3 CH2Rl in which Rl is hydrogen or methyl, R4 and R5 independently of one another are Cl-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Xa OH
. R r ~3/ 3 (l~ ( )n \._ ~ 2 (Xa)
L-CO- (II) in which L is hydrogen, Cl-Cl2-alkyl, C2-Cl2-alkenyl, C3-C4-alkynyl, C3-C12-cycloalkyl, C7-C14-alkaryl, C7-C14-aralkyl, chloro-methyl, unsubstiLuted phenyl, phenyl which is substituted by two Cl-C4-alkyls and one hydroxyl, or a group -ORg, in which Rg is Cl-C12-alkyl, cyclohexyl, C2-C12-alkenyl, benzyl or phenyl, or L is a group of the formula III
R3 ~ 4 ( )m \ / (III) \R5 or R2 is a group of the formula IV
C ~ lO (IV) o 1 1 in which Rlo and Rll independently of one another are Cl-Cl2-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-Cl4-aralkyl and Rll additionally can also be hydrogen, or R2 is a group of the formula V
~4675 ~H
R 4\ ~ \ / 5 -CH2-CH(R12)-SY-C)-(A') (V) in which A' is methylene or a group -CH2-CH(R13)- and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenyl, or R2 is a group of the formula VI
1 2\./. 3 0 R4\ ~!, /R5 -B-~ (y-c)n-(A) il (VI) ~ R3 in which B is a group CrH2r, in which r is a number from 2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, phenylene, xylylene, bitolylene, C5-C12-cycloalkylene o~ a group -CONH-Bl-NHCO-, in which Bl is a group CrH2r, phenylene, nahpthylene, tolylene or a group of the formulae CH3 \ /. , ~ -C~ -- or -.\ \--C--/ \.
CH3 R R' R" R R' R"
in which R' is hydrogen, methyl or ethyl, R" is hydrogen or methyl and r is a defined above, or R2 is one of the groups -S(O) R14 or -OR15, in which z is the number 1 or 2, Rl4 i9 Cl-C12-alkyl, C7-C14-alkaryl or phenyl and Rl5 is Cl-C12-alkyl, C3 C12 a Y ' 7 14 aralkyl or a group of the formula L'-CO-, in which L' is as defined above for L, R4 and R5 independently of one another are Cl-C12-alkyl, C3-C12-cycloalkyl, C7-C14-aralkyl, C7-C14 alkaryl or phenyl and R4 can additionally also be hydrogen or a group of the formula Ia :1214f~75 OH
~ ~ (A) (Rc-y)- .' ~ -R (la) CH~ CH2Rl in which Rl, R2, R3, R5, A, Y, m and n are as defined and M is a direct bond, -8-~ s s s ~ s -CH -S-CH --CH2-O-CH2-, -O- and -N(D3)-, and Dl and D2 independently of one another are hydrogen, Cl-C18-alkyl, alkyl interrupted by 1 to 3 -S- or phenyl, or Dl and D2, together with the C atom linking the~, form a 5-membered or 6-membered aliphatic ring and D3 is hydrogen, Cl-C18-alkyl or phenyl, Y i9 -O-, n and m independently of one another are zero or 1, and A is methylene or a group -CH2-CH(R20)-or -CH2-C(E)(G)-, in which R20 is hydrogen, methyl, ethyl, phenoxy-methyl or phenyl, E is cyano or a group -C(O)OR21, -C(O)R22, -S02R22, -P(O)(OR23)2, -C(O)NR24R25 or -CHO, in which R21 is 1 4 Y ~ 22 ig ~1 C12-alkyl, C7-C14-alkaryl or phenyl 9 R
i9 Cl-C18-alkyl, phenyl or allyl, and R24 and R25 independently of one another are hydrogen, Cl-C18-alkyl or phenyl, and G is hydrogen, Cl-C18-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-cl8-alkylcycloalkvl~ C6-C14-cycloalkylalkyl. C7-C14-aralkyl, C7-Clg-alkyl-aralkyl, phenyl, or Cl-C18-alkyl which is substituted by phenoxy, C7-C10-alkylphenoxy, benzyloxy, cyclohexyloxy, cyano, -COOR26, -OCOR27 or -P(O)(OR28)2, R26 being Cl-C18-alkyl, C3-C12-cycloalkyl or a group of the formula VII
~;~1467~
1\,~3./ 2 1 _. (VII) C~3 CH2R
R27 being Cl-C18-alkyl, c3-C12-cycloalkYl, phenyl, C7-C14~aralkYl or a group of the formula III and R28 being Cl-C18-alkyl, allyl or phenyl, or G is C2-C18-alkyl interrupted by -O-, -S-, -SO- or -SO2-, a group of the formula VII or a group of the formula 2 \ ~--OH
=.
~ 30 in which R29 and R30 independently of one another are Cl-C4-alkyl and R30 additionally can also be hydrogen, or, if E is a group -C(O)R22, G and R22 together are trimethylene or tetramethylene.
Cl-C12-Alkyl substituents which may be present can be branched or unbranched alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, n-pentyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-nonyl, decyl or dodecyl. Cl-C4-Alkyl is preferred. cl-Cl~-AlkYl radicalg R16 and R23 can additionally be, for example, tridecyl, tetradecyl9 hexadecyl or octadecyl.
Cl-C4-Alkyl substituents which may be present are methyl,ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or tert.-butyl.
C3-C12-Alkenyl substituents which may be present are, for example, allyl, methallyl, 2-butenyl, Z-hexenyl, 2-octenyl, 4-octenyl, 2-decenyl or 2-dodecenyl. Allyl is preferred. C2-C12-Alkenyl substituents can additionally also be vinyl. In this case, vinyl and allyl are preferred.
C
~, ~4~;7X
C3-C4-Alkynyl radicals R2, G and L are, for example, propargyl, n-but-l-ynyl or n-but-2-ynyl.
Propargyl is preferred.
C3-Cll-Alkoxyalkyl radicals R2 are, for exa~ple, ethoxymethyl, 2--me-thoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 2-n-butoxypropyl, 2-n-octoxyethyl, 3-n-octoxypropyl or 6-n-butoxyhexyl. Additionally, a C2-alkoxyalkyl radical R2~can also be methoxymethyl.
Halogens Xl and X2 are, for example, bromine, iodine and in particular chlorine.
C3-C12-Cycloalkyl substituents which may be present are, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, -methyl-cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, or cyclododecyl.
Cyclohexyl is preferred.
C7-C14-Alkaryl substituents which may be present are, for example, phenyl substituted by Cl-C4-alkyl, such as p-tolyl, 2,4-dimethyl-phenyl, 2,6-dimethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 4-tert.-butylphenyl, 2,4-di-tert.-butylphenyl or 2,6-di-tert.-butylphenyl. 2,4-Di-tert.-butylphenyl and 2,4-dimethylphenyl are preferred.
5-Membered or 6-membered heterocyclic rings, fonmod by R7 and R8 together with the nitrogen atom to which they are bonded, are, for example, pyrrolidine, oxazolidine, piperidine or morpholine radicals.
C7-C14-Aralkyl substituents which may be present are, for example, benzyl, p-methylbenæyl, p-tert.-butylbenzyl, l-phenylethyl, dimethylbenzyl or 2-phenylethyl.
~2~467~
In -C H2 ~ groups B or Bl in which r is a number between 1 and 12, r preferably is a number between 2 and 8. Examples are methylene, ethylene, trimethylene, tetramethylene, hexamethylene, ortanethylene, nonamethylene, 2,2,4-trimethylhexamethylene, decamethylene and dodecamethylene.
C4-C8-Alkenylene radicals B are, for example, but-2-en-1,4--ylene.
C4-C8-Alkynylene radicals B are, for example, but-2-yn-1,4-ylene.
C5-C12-Cycloalkylene radicals B are, for example, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene or cyclododecylene.
Cyclohexylene is preferred.
Cl-C12-Alkyl radicals G, substituted by phenoxy, benzyloxy, cyclo-hexyloxy or cyano, can, for example, be one of the following radicals: 2-phenoxyethyl, 2-ben~yloxyethyl, cyclohexyloxymethyl, 2-cyanoethyl, cyanomethyl or 3-cyanopropyl.
C6-C18-Alkylcycloalkyl radicals G are, for example, methylcyclo-hexyl, ethylcyclohexyl, butylcyclohexyl, tert.-butylcyclohexyl, dodecylcyclohexyl, ethylcyclopentyl or butylcyclopentyl and C6-Cl4-cycloalkylalkyl radicals G are, for example, cyclohexylme-thyl, cyclohexylethyl, cyclohexylbutyl, cyclohexylhexyl, cyclo-hexyloctyl, cyclopentyipropyl or cyclopenthylhexyl.
Cl-C18-Alkyl radicals G, substituted by C7-C10-alkylphenoxy, can be, for example, p-methylphenoxymethyl, p-methylphenoxyethyl, p-methylphenoxypropyl, p-tert.-butylphenoxymethyl, p-tert.-butylphenoxyethyl, 2,4-dimethylphenoxymethyl, 2,4-dimethylphenoxy-ethyl, 2,4-di-tert.-butylphenoxyethyl, 2,6-di-tert.-butylphenoxy-methyl or 2,4,6-trimethylphenoxyethyl.
~;~14ti7~
C2-C12-Alkyl radicals G interrupted by -O-, -S-, -SO- or -SO2-are, for example, one of the following radicals: methoxymethyl, 2-butoxyethyl, 2-octyloxyethyl, isopropoxymethyl, 3-butylthiopropyl, 2-decylthioethyl, 2-(isohexylsulfinyl)-ethyl, 2-(butylsulfonyl)-ethyl or 2-(ethylsulfonyl)-propyl.
Those colour-photographic recording materials are preferred which contain, as the light stabiliser, at least one compound of the formula X
4\._. 1\.~3./ 2 1 \ / ( )m ( )n \ ~ 2 (X) R5 C~3 CH2Rl in which Rl is hydrogen or methyl, R4 and R5 independently of one another are Cl-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Xa OH
. R r ~3/ 3 (l~ ( )n \._ ~ 2 (Xa)
3 3 in which M is a direct bond, -CH(D2)- or -S- and D2 is hydrogen or Cl-C8-alkyl, A is methylene, ethylene or a group -CH2-C(E)(C)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen, Cl-Cl8-alkyl, allyl, cyclohexyl, benzyl or one of the two groups of the formulae 1;21467S
.~.3/ 3 /C~CH3)3 \._.~ 2 and 2 \.=./
C~8 CH8 ~30 in which R30 is methyl or tert.-butyl, or E and G together form a group -CO-(C112)4-, n and m are as defined above, R2 is hydroxyl, Cl-C4-alkyl, allyl, methallyl, propargyl, benzyl, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of the formula -(CH2) -CH(R6)-Xl or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3~ Xl is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)R7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R~)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, Cl-C8-alkyl, vinyl, allyl, methallyl, C5-C8-cycloalkyl, phenyl or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, Cl-C4-alkyl, vinyl, allyl, cyclohexyl, phenyl, benzyl, chloromethyl or a group -ORg, in which R9 is Cl-C8-alkyl, cyclohexyl, vinyl, allyl or methallyl, or L is a group of the formula III, in which m, A, R4 and R5 are defined for these preferred compounds, and R3 is hydrogen, or R2 is a group of the formula IV, in which Rlo and Rll independently of one another are Cl-C12-alkyl, cyclohexyl or phenyl and Rll additionally can also be hydrogen, or R2 is a group of the formula XI
-CH2-CH(Rl2)-(Y-C) -(A') -~ -OH (XI) \R5 in which n, R4, R5 and Y are as defined for these preferred compounds,A' is methylene or a group -CH2-CH(R13)-, q is zero or l, and R12 and R13 independently of one another are hydrogen or methyl, or R2 is a group of the formula XII
~Z14675 CH3\ /CH3 ~ 4 -B- ~ \--(Y-C~) -(A) --~ ~--OH (XII) \R5 in which A, R4, R5, Y, n and m are as defined for these preferred compounds and B is a group --~CH2~ or -CON~-~CH2~-NHCO-, in which r is one of the numbers 2 to 8, or C4-C8-alkenylene, xylylene or bitolylene, or R2 is one of the ~roups -SO2R14 or -OR15, in which R14 is Cl-C4-alkyl, p-tolyl or phenyl and R15 is Cl-C4-alkyl, benzyl or a group of the formula L'-CO-, in which L' is as already defined for L in these preferred compounds, and Y is -O-.
Those colour-photographic recording materials are particularly preferred which contain, as the light stabiliser, at least one compound of the formula XIV
.~.3/ 3 /C~CH3)3 \._.~ 2 and 2 \.=./
C~8 CH8 ~30 in which R30 is methyl or tert.-butyl, or E and G together form a group -CO-(C112)4-, n and m are as defined above, R2 is hydroxyl, Cl-C4-alkyl, allyl, methallyl, propargyl, benzyl, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of the formula -(CH2) -CH(R6)-Xl or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3~ Xl is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)R7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R~)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, Cl-C8-alkyl, vinyl, allyl, methallyl, C5-C8-cycloalkyl, phenyl or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, Cl-C4-alkyl, vinyl, allyl, cyclohexyl, phenyl, benzyl, chloromethyl or a group -ORg, in which R9 is Cl-C8-alkyl, cyclohexyl, vinyl, allyl or methallyl, or L is a group of the formula III, in which m, A, R4 and R5 are defined for these preferred compounds, and R3 is hydrogen, or R2 is a group of the formula IV, in which Rlo and Rll independently of one another are Cl-C12-alkyl, cyclohexyl or phenyl and Rll additionally can also be hydrogen, or R2 is a group of the formula XI
-CH2-CH(Rl2)-(Y-C) -(A') -~ -OH (XI) \R5 in which n, R4, R5 and Y are as defined for these preferred compounds,A' is methylene or a group -CH2-CH(R13)-, q is zero or l, and R12 and R13 independently of one another are hydrogen or methyl, or R2 is a group of the formula XII
~Z14675 CH3\ /CH3 ~ 4 -B- ~ \--(Y-C~) -(A) --~ ~--OH (XII) \R5 in which A, R4, R5, Y, n and m are as defined for these preferred compounds and B is a group --~CH2~ or -CON~-~CH2~-NHCO-, in which r is one of the numbers 2 to 8, or C4-C8-alkenylene, xylylene or bitolylene, or R2 is one of the ~roups -SO2R14 or -OR15, in which R14 is Cl-C4-alkyl, p-tolyl or phenyl and R15 is Cl-C4-alkyl, benzyl or a group of the formula L'-CO-, in which L' is as already defined for L in these preferred compounds, and Y is -O-.
Those colour-photographic recording materials are particularly preferred which contain, as the light stabiliser, at least one compound of the formula XIV
4\,_. o .~3./ 3 \.,./ ( )m \ ~ 2 (XIV) in which m is zero or 1, A is methylene or ethylene, R4 and R5 independently of one another are methyl or tert.-butyl, Y is -O-, and R2 is hydroxyl, me~hyl, allyl, benzyl, 2-hydroxyethyl, acetyl, acryloyl, methoxy, acetoxy or a group of the formula XV
O ._./ 4 -C-(A) ~ ~- OH (XV) \R
`.~
~;~1467S
in which m, A, R4 and R5 are as defined for these preferred com-pounds, or is a group of the formula IV, in which Rlo is Cl-C8-alkyl, cyclohexyl or phenyl and Rll is hydrogen, Cl-C8-alkyl or cyclohexyl.
Those colour-photographic recording materials are also particularly preferred which contain, as the light stabiliser, at least one compound of the formula XIV, in which R2 is a group of the formula O /C(CH3)3 -CH CH -OC-~ OH
C(CH3)3 and m, A, R4, R5 and Y are as def;ned in the last definition of preferred compounds, as well as those colour-photographic recording materials which contain, as the light stabiliser, at least one compound of the formula XIV, in which A is a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or COOCH3 and G is hydrogen or one of the two groups of the formulae , ~3./ 3 /C(CH3)3 \ ~ -R2 and -CH -~ OH
; 3 C(CH3)3 or E and G together form a group -CO-(CH2)4-, R2 is -CHO, acetyl or acryloyl and m, R4, R5 and Y are as defined in the last definition of preferred compounds.
Also of interest are colour-photographic recording materials which contain, as the light stabiliser, at least one compound of the formula I, in which A is a group -CH2-C(E)(G)-, m and n are the S - ,1 `'~
h J
lZ14675 2 5 OH, S02R14, -OR15 or a group of the formulae V or VI. These compounds are also novel. They can likewise be prepared by ~ethods known per se and according to the equation 4~ 3 ~ 11 1\.~3./ 2 1 HO--\ ~ + HC-C-Y--\ ~-R2 =- I ---R5 2 ~ CH3 CH2R
4\._. ~R3 HO--~ ~ E Rl~C ~ CH2R
R5 CH -C-C-Y-- \N-R
G C~3 CH2Rl T being a group -N(R)2, -SC(S)N(R)2 or -OR, in which R is methyl or ethyl, R2 being -OH, -S02-R14, -OR15 or a group of the formulae V ~r VI and Rl, R3, R4, R5, E, G and Y being as defined above.
In a variant, it is possible to prepare the compounds mentioned by known reactions on the ring nitrogen of the compound of the formula R4\
HO-.~ ~ O Rl\C~3/CH2Rl / (A)m-(C-Y)n--\ N-H
CH2Rl for example by alkylation, acylation or addition.
Ihe starting substances and the other compounds of the fonmula I
''' '' ' are known. If some of these should still be novel, they can be prepared analogously to methods known per se.
Typical representatives of the compounds of the formula I are listed in Tables I to V which follow.
14~;75 . ,i.~
sD~ r ~ , .~ ~O O O O O O O O
~ ~ r ~
lZ1467~
1 11 ~: X U~ , ,, P~ I~ ~ I~ Z ~ iC~l c~l ~ 0o 3rl ;jl~ ~ t 3,~ ", ~ O O O O O O
c o~ lr 1 ,- '.~ I _ 1;214675 ~\ A " ~ ,, o ~ ~' ~ . ~ ~ T
67~i .
g ~
, .
Table II
. ,~
( 3)3 ~ 3./ 3 H0--~ (CH2t---C00--~ ~ 2 R/ C/H3\CH3 , _ . .
Light 4 n R
stabiliser _ .
19 -H 2 -C0-CH=CH2 24 -H 2 -C0-CH3 /C(CH3)3 -C(CH3)3 0 2 ~ \ ~ /
26 -C(CH3)3 0 -C0-CH=CH2 27 C~CH~ ~ -CO-CM~CH2 ~, ~21~675i Table III
_ . .
~CH3)3 ~ E ~ 3./ 3 HO-~ -CH2-C-COO--\~ 2 (CH3~3c G C~ \CH
L ght G R2 _ . _ .
28 -CN/C(CH3)3 -CXO
29 -CO-CH(CH3)3 -CO-CH
-COOCH3 -CH2--~ ~ -OH -CO-CH3 31 -CN-CH --~ ~ -OH -CO-CH~CH2 32 -CN \ ;~ 2 2 -CO-CH-CH2 , 12~L4675 Table IV
. ~
(CH3)3C\ /o~ \ /C(CH3)3 i1 i i i1 \ ;)2 (~H;)2 . _ 3/CH3 CH3-C0~ ~~~ C00 \ ~ -C0-CH3 C~ \CH C~3\CH3 _ .
Light stabiliser No. M
. . _ . . .. ~
36 direct bond . .. .. ~
1A~>14675 Table V
~-(CH2 ~ ( 2)n ~
CH / \ CH i/ \ CH
~ C/H3 ~ \CH3 Light ~ . .
stabiliser n R R2 _ l /C(CH3)3 37 2 2 2 \.=.\ -C0-CH3 ~ 3 2 2 \ , / ~ O~
The compounds of the formula I are scarcely soluble in water and, for this reason~ they are dissolved in a low-boiling organic solvent, such as methyl acetate, ethyl acetate, carbon tetrachlo-ride, chloroform, methanol, ethanol, n-butanol, dioxane, acetone or benzene, in a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dimethyl sulfoxide, di-n-butyl phthalate or ethyl N-diphenylcarbamate, or in a solvent mixture consisting of the abovementioned low-boiling and high-boiling organic solvents, the solution obtained is added to a protective colloid solution, such as especially an aqueous gelatine solution, 14~75 and the mixture is dispersed by means of a colloid mill, a homoge-niser or by applying ultrasonics.
The dispersions thus obtained are then used for the preparation of the layers of colour-photographic recording materials. These layers can, for example, be interlayers or protective layers, but especially light-sensitive (for example blue-sensitive, green-sensitive and red-sensitive) silver halide emulsion layers in which, when the exposed recording material is developed, cyan dyes, magenta dyes and yellow dyes are formed from the corresponding colour couplers.
If desired, the light stabiliser can also be applied in the treatment baths which are used after colour development, for example in fixing baths and/cr washing baths, but a certain solubility of the compounds of the formula I in alcohols (methanol/ethanol), aqueous alkali and/or water is necessary in that case. If the diffusion transfer method is used, the light stabiliser can be incorporated not only into the customary photographic emulsion layers, but also into a receiving layer.
It is pos~ible to employ any desired cyan couplers, magenta couplers and yellow couplers, which are used for the formation of the said dyes and hence the colour images. They can be dissolved, for example, in an alkaline solution or in a high-boiling organic solvent, these solutions then being dispersed in an aqueous gelatine solution and being incorporated into a photographic silver halide emulsion.
They can also be added the colour-photographic developers.
In the photographic recording material according to the present invention, the light stabilisers according to formula I can be combined in the same layer not only with the colour couplers, but additionally also with ultra-violet absorbers.
The silver halide emulsions preferably contain gelatine as the binder, if appropriate as a mixture with other high-molecular natural or synthetic compounds.
The silver halide emulsions can, for example, be silver bromide emulsions, silver chloride emulsions or silver iodide emulsions, or they can also be those emulsions which contain a mixture of silver halides, for example silver bromide/iodide emulsions or silver chloride/bromide emulsions.
The emulsions can be sensitised chemically, and they can also contain customary organic stabilisers and anti-fogging agents as well as customary plasticisers, for example glycerol. The emulsions can also be hardened with the hardeners customary for gelatine. ~oreover, the emulsions can contain customary coating assistants. The emulsions can be applied to customary bases for photographic recording material.
To develop the colour-photographic recording material, the customary developer baths can be used. As a rule, these contain a developer substance of che p-phenylenediamine type, a development retarder, such as potassium bromide, an antioxidant, such as sodium sulfite, and a base, for example an alkali metal hydroxide or alkali metal 1~14675 carbonate. The developing baths can also contain a customary anti-fogging agent and complexing agents.
The light stabilisers to be used according to the invention are in certain cases also suitable for protecting colour-photographic layers, in which the dyes are incorporated directly into the emulsion and the image is produced by selective bLeaching.
The quantity of light stabiliser, if appropriate in combination with a customary ultraviolet absorber~ can vary within wide limits and is approximately within the range from l to 2,000 mg, preferably l to 800 and in particular 400 mg, per m of the layer into which it is (or they are) incorporated.
If the photographic material contains an agent which absorbs W
light, this agent can be present in the same layer or in the adjacent layer.
The ultraviolet absorber can be present in one layer, together with the light stabiliser, or in an adjacent layer. The weight ratio between a customary ultraviolet absorber and the light stabiliser of the formula I is about (5-10):1, and the molar ratio is about (10-20):1. Examples of ultraviolet absorbers are compounds of the ben20phenone, acrylonitrile, ~hiazolidone, benzotriazole, oxazole, thiazole and imidazole type.
The colour images obtained with the recording material according to the invention by exposure and development display very good lightfastness to visible and ultraviolet light. The compounds of the formula I are virtually colourless, so that there is no discolouration of the images; additionally, they are well compatible lZ~4675 with the customary photographic additives present in the individual layers; due to their high effectiveness, the quantity in which they are used can be reduced, and they are thus prevented from precipi-tating or crystallising out, when they are incorporated as an organic solution into the aqueous binder emulsions which are used for the preparation of photographic layers. The individual processing steps, necessary after the exposure of the photographic recording material, for the production of the colour images are not adversely affected by the light stabilisers. Moreover, the formation of so-called abrasion fog, which frequently occurs in the case of blue-sensitive emulsions, can be largely suppressed. This abrasion fog can, for example, occur if mechanical stresses, for example turning, bending or rubbing, are exerted in photographic materials (silver halide emulsion layers present on a base of natural or synthetic materials) during manufacture or during treatment before development (T.H. James, The Theory of the Photographic Process, 4th e ition, Macmillan, New York, N.Y. 1977, pages 23 et seq. and pages 166 et seq.) The examples which follow explain the present invention, without restricting it.
Example 1: 10.8 g of 2,2,6,6-tetramethyl-4-piperidinyl cyanoacetate and 35 g of 2,6-di-tert.-butyl-4-hydroxy-benzyl N,N-diethyl-dithiocarbamate are introduced into 150 ml o~ isop~opanol and the mixture is heated to 50C. ~t this temperature, a solution of 3.8 g of sodium hydroxide in 20 ml of water i5 added dropwise in the course of 30 minutes. The light-brown solution is further stirred at 50-60~C and then refluxed for 1.5 hours. The green solution is cooled to room temperature, 200 ml of water are added and the solu-tion is then cooled to 5C. The light-yellow product which has ~' `i ~, j 4Çi7~
precipitated is filtered off with suction, washed with cold isopropanol (aqueous) and dried. Melting point 174C. This product is dissolved in 150 ml of acetonitrile. 1.5 g of triethylamine are added and the solution is warmed to 60C. 1.0 g of acrylic acid chloride is added dropwise and the mixture is stirred for one further hour after the addition. The reaction mixture is filtered and the filtrate is evaporated. After purification by column chromatography l-acryloyl-2,2,6,6-tetramethylpiperidin-4-yl ~-(3,5-di-tert.-butyl-4-hydroxybenzyl)-~-cyano-~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate is obtained. Melting point 188-190C
(light stabiliser No. 31).
Application Examples Example 2a and b 0.087 g of the yellow coupler of the formula CH C~
CH3-c-cocHcoNH-~ C5 11 CH3 l NHC0(CH2)3-~\ / C5 11( ~ S 2 \ _ / 3 (CH3)2HC
and 0.026 g of one of the light stabilisers indicated in the tables which follow are dissolved in 2.0 ml of a mixture of tricresyl phosphate and ethyl acetate (1.5 g in 100 ml). To this solution, 7.0 ml of a 6~ gelatine solution, 0.5 ml of an 8~ solution of the wetting agent of the formula ï4675 3 1 2 1 \ / 2 2 )3 3 in (3:4) isopropanoL/water and O.S ml of water are added, and thewhole is emulsified ultrasonically for S minutes at a power of 100 watt.
2.0 ml of a silver bromide emulsion having a silver content of 6.o g per litre, 0.7 ml of a 1 % aqueous solution of the hardener of the formula ~._N ._ .
\ ~ NH--\ /-~S03Na and 3.8 ml of water are added to 2.5 ml of the emulsion thus obtained, and the mixture is adjusted to a pH value of 6.5 and coated onto subbed, plastic-coated, white paper mounted on a glass plate.
After solidification, the paper is dried at room temperature in a circulating-air oven.
After 3 days, samples cut to 35 x 180 mm are exposed behind a step wedge at 3,000 lux x seconds and then processed by the Kodak Ektaprint 2~Dprocess.
a) One part of the yellow wedges thus obtained is irradiated in an Atlas Weather-O-meter with a 2,500 W xenon lamp behind a W filter (Kodak 2C) with 63 KJoule/cm2 and a second part is irradiated with 168 KJoule/cm (one further comparative sample of each does not contain any light stabiliser).
The table shows the percentage decrease in density, the original 4f~7S
density being 1.0:
With W filter _ _ Light stabiliser Density loss at 440 nm in percent No. (D = 1.0), quantity of light 63 KJ/cm 168 KJ/cm L ~7 ~
b) A part of the yellow wedges obtained is irradiated as described under a~ but without a W filter, with 21 KJoule/cm and a further part is irradiated, likewise without a W filter, with 63 KJoule/cm (one further comparative sample of each does not contain any light stabiliser).
The table shows the percentage decrease in density, the original density being 1.0:
Without W filter Light stabiliser Density loss at 440 nm in percent No. (D - 1.0), quantity of light 21 KJ14Cm2 ¦ 63 KJ/cm .
O ._./ 4 -C-(A) ~ ~- OH (XV) \R
`.~
~;~1467S
in which m, A, R4 and R5 are as defined for these preferred com-pounds, or is a group of the formula IV, in which Rlo is Cl-C8-alkyl, cyclohexyl or phenyl and Rll is hydrogen, Cl-C8-alkyl or cyclohexyl.
Those colour-photographic recording materials are also particularly preferred which contain, as the light stabiliser, at least one compound of the formula XIV, in which R2 is a group of the formula O /C(CH3)3 -CH CH -OC-~ OH
C(CH3)3 and m, A, R4, R5 and Y are as def;ned in the last definition of preferred compounds, as well as those colour-photographic recording materials which contain, as the light stabiliser, at least one compound of the formula XIV, in which A is a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or COOCH3 and G is hydrogen or one of the two groups of the formulae , ~3./ 3 /C(CH3)3 \ ~ -R2 and -CH -~ OH
; 3 C(CH3)3 or E and G together form a group -CO-(CH2)4-, R2 is -CHO, acetyl or acryloyl and m, R4, R5 and Y are as defined in the last definition of preferred compounds.
Also of interest are colour-photographic recording materials which contain, as the light stabiliser, at least one compound of the formula I, in which A is a group -CH2-C(E)(G)-, m and n are the S - ,1 `'~
h J
lZ14675 2 5 OH, S02R14, -OR15 or a group of the formulae V or VI. These compounds are also novel. They can likewise be prepared by ~ethods known per se and according to the equation 4~ 3 ~ 11 1\.~3./ 2 1 HO--\ ~ + HC-C-Y--\ ~-R2 =- I ---R5 2 ~ CH3 CH2R
4\._. ~R3 HO--~ ~ E Rl~C ~ CH2R
R5 CH -C-C-Y-- \N-R
G C~3 CH2Rl T being a group -N(R)2, -SC(S)N(R)2 or -OR, in which R is methyl or ethyl, R2 being -OH, -S02-R14, -OR15 or a group of the formulae V ~r VI and Rl, R3, R4, R5, E, G and Y being as defined above.
In a variant, it is possible to prepare the compounds mentioned by known reactions on the ring nitrogen of the compound of the formula R4\
HO-.~ ~ O Rl\C~3/CH2Rl / (A)m-(C-Y)n--\ N-H
CH2Rl for example by alkylation, acylation or addition.
Ihe starting substances and the other compounds of the fonmula I
''' '' ' are known. If some of these should still be novel, they can be prepared analogously to methods known per se.
Typical representatives of the compounds of the formula I are listed in Tables I to V which follow.
14~;75 . ,i.~
sD~ r ~ , .~ ~O O O O O O O O
~ ~ r ~
lZ1467~
1 11 ~: X U~ , ,, P~ I~ ~ I~ Z ~ iC~l c~l ~ 0o 3rl ;jl~ ~ t 3,~ ", ~ O O O O O O
c o~ lr 1 ,- '.~ I _ 1;214675 ~\ A " ~ ,, o ~ ~' ~ . ~ ~ T
67~i .
g ~
, .
Table II
. ,~
( 3)3 ~ 3./ 3 H0--~ (CH2t---C00--~ ~ 2 R/ C/H3\CH3 , _ . .
Light 4 n R
stabiliser _ .
19 -H 2 -C0-CH=CH2 24 -H 2 -C0-CH3 /C(CH3)3 -C(CH3)3 0 2 ~ \ ~ /
26 -C(CH3)3 0 -C0-CH=CH2 27 C~CH~ ~ -CO-CM~CH2 ~, ~21~675i Table III
_ . .
~CH3)3 ~ E ~ 3./ 3 HO-~ -CH2-C-COO--\~ 2 (CH3~3c G C~ \CH
L ght G R2 _ . _ .
28 -CN/C(CH3)3 -CXO
29 -CO-CH(CH3)3 -CO-CH
-COOCH3 -CH2--~ ~ -OH -CO-CH3 31 -CN-CH --~ ~ -OH -CO-CH~CH2 32 -CN \ ;~ 2 2 -CO-CH-CH2 , 12~L4675 Table IV
. ~
(CH3)3C\ /o~ \ /C(CH3)3 i1 i i i1 \ ;)2 (~H;)2 . _ 3/CH3 CH3-C0~ ~~~ C00 \ ~ -C0-CH3 C~ \CH C~3\CH3 _ .
Light stabiliser No. M
. . _ . . .. ~
36 direct bond . .. .. ~
1A~>14675 Table V
~-(CH2 ~ ( 2)n ~
CH / \ CH i/ \ CH
~ C/H3 ~ \CH3 Light ~ . .
stabiliser n R R2 _ l /C(CH3)3 37 2 2 2 \.=.\ -C0-CH3 ~ 3 2 2 \ , / ~ O~
The compounds of the formula I are scarcely soluble in water and, for this reason~ they are dissolved in a low-boiling organic solvent, such as methyl acetate, ethyl acetate, carbon tetrachlo-ride, chloroform, methanol, ethanol, n-butanol, dioxane, acetone or benzene, in a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dimethyl sulfoxide, di-n-butyl phthalate or ethyl N-diphenylcarbamate, or in a solvent mixture consisting of the abovementioned low-boiling and high-boiling organic solvents, the solution obtained is added to a protective colloid solution, such as especially an aqueous gelatine solution, 14~75 and the mixture is dispersed by means of a colloid mill, a homoge-niser or by applying ultrasonics.
The dispersions thus obtained are then used for the preparation of the layers of colour-photographic recording materials. These layers can, for example, be interlayers or protective layers, but especially light-sensitive (for example blue-sensitive, green-sensitive and red-sensitive) silver halide emulsion layers in which, when the exposed recording material is developed, cyan dyes, magenta dyes and yellow dyes are formed from the corresponding colour couplers.
If desired, the light stabiliser can also be applied in the treatment baths which are used after colour development, for example in fixing baths and/cr washing baths, but a certain solubility of the compounds of the formula I in alcohols (methanol/ethanol), aqueous alkali and/or water is necessary in that case. If the diffusion transfer method is used, the light stabiliser can be incorporated not only into the customary photographic emulsion layers, but also into a receiving layer.
It is pos~ible to employ any desired cyan couplers, magenta couplers and yellow couplers, which are used for the formation of the said dyes and hence the colour images. They can be dissolved, for example, in an alkaline solution or in a high-boiling organic solvent, these solutions then being dispersed in an aqueous gelatine solution and being incorporated into a photographic silver halide emulsion.
They can also be added the colour-photographic developers.
In the photographic recording material according to the present invention, the light stabilisers according to formula I can be combined in the same layer not only with the colour couplers, but additionally also with ultra-violet absorbers.
The silver halide emulsions preferably contain gelatine as the binder, if appropriate as a mixture with other high-molecular natural or synthetic compounds.
The silver halide emulsions can, for example, be silver bromide emulsions, silver chloride emulsions or silver iodide emulsions, or they can also be those emulsions which contain a mixture of silver halides, for example silver bromide/iodide emulsions or silver chloride/bromide emulsions.
The emulsions can be sensitised chemically, and they can also contain customary organic stabilisers and anti-fogging agents as well as customary plasticisers, for example glycerol. The emulsions can also be hardened with the hardeners customary for gelatine. ~oreover, the emulsions can contain customary coating assistants. The emulsions can be applied to customary bases for photographic recording material.
To develop the colour-photographic recording material, the customary developer baths can be used. As a rule, these contain a developer substance of che p-phenylenediamine type, a development retarder, such as potassium bromide, an antioxidant, such as sodium sulfite, and a base, for example an alkali metal hydroxide or alkali metal 1~14675 carbonate. The developing baths can also contain a customary anti-fogging agent and complexing agents.
The light stabilisers to be used according to the invention are in certain cases also suitable for protecting colour-photographic layers, in which the dyes are incorporated directly into the emulsion and the image is produced by selective bLeaching.
The quantity of light stabiliser, if appropriate in combination with a customary ultraviolet absorber~ can vary within wide limits and is approximately within the range from l to 2,000 mg, preferably l to 800 and in particular 400 mg, per m of the layer into which it is (or they are) incorporated.
If the photographic material contains an agent which absorbs W
light, this agent can be present in the same layer or in the adjacent layer.
The ultraviolet absorber can be present in one layer, together with the light stabiliser, or in an adjacent layer. The weight ratio between a customary ultraviolet absorber and the light stabiliser of the formula I is about (5-10):1, and the molar ratio is about (10-20):1. Examples of ultraviolet absorbers are compounds of the ben20phenone, acrylonitrile, ~hiazolidone, benzotriazole, oxazole, thiazole and imidazole type.
The colour images obtained with the recording material according to the invention by exposure and development display very good lightfastness to visible and ultraviolet light. The compounds of the formula I are virtually colourless, so that there is no discolouration of the images; additionally, they are well compatible lZ~4675 with the customary photographic additives present in the individual layers; due to their high effectiveness, the quantity in which they are used can be reduced, and they are thus prevented from precipi-tating or crystallising out, when they are incorporated as an organic solution into the aqueous binder emulsions which are used for the preparation of photographic layers. The individual processing steps, necessary after the exposure of the photographic recording material, for the production of the colour images are not adversely affected by the light stabilisers. Moreover, the formation of so-called abrasion fog, which frequently occurs in the case of blue-sensitive emulsions, can be largely suppressed. This abrasion fog can, for example, occur if mechanical stresses, for example turning, bending or rubbing, are exerted in photographic materials (silver halide emulsion layers present on a base of natural or synthetic materials) during manufacture or during treatment before development (T.H. James, The Theory of the Photographic Process, 4th e ition, Macmillan, New York, N.Y. 1977, pages 23 et seq. and pages 166 et seq.) The examples which follow explain the present invention, without restricting it.
Example 1: 10.8 g of 2,2,6,6-tetramethyl-4-piperidinyl cyanoacetate and 35 g of 2,6-di-tert.-butyl-4-hydroxy-benzyl N,N-diethyl-dithiocarbamate are introduced into 150 ml o~ isop~opanol and the mixture is heated to 50C. ~t this temperature, a solution of 3.8 g of sodium hydroxide in 20 ml of water i5 added dropwise in the course of 30 minutes. The light-brown solution is further stirred at 50-60~C and then refluxed for 1.5 hours. The green solution is cooled to room temperature, 200 ml of water are added and the solu-tion is then cooled to 5C. The light-yellow product which has ~' `i ~, j 4Çi7~
precipitated is filtered off with suction, washed with cold isopropanol (aqueous) and dried. Melting point 174C. This product is dissolved in 150 ml of acetonitrile. 1.5 g of triethylamine are added and the solution is warmed to 60C. 1.0 g of acrylic acid chloride is added dropwise and the mixture is stirred for one further hour after the addition. The reaction mixture is filtered and the filtrate is evaporated. After purification by column chromatography l-acryloyl-2,2,6,6-tetramethylpiperidin-4-yl ~-(3,5-di-tert.-butyl-4-hydroxybenzyl)-~-cyano-~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate is obtained. Melting point 188-190C
(light stabiliser No. 31).
Application Examples Example 2a and b 0.087 g of the yellow coupler of the formula CH C~
CH3-c-cocHcoNH-~ C5 11 CH3 l NHC0(CH2)3-~\ / C5 11( ~ S 2 \ _ / 3 (CH3)2HC
and 0.026 g of one of the light stabilisers indicated in the tables which follow are dissolved in 2.0 ml of a mixture of tricresyl phosphate and ethyl acetate (1.5 g in 100 ml). To this solution, 7.0 ml of a 6~ gelatine solution, 0.5 ml of an 8~ solution of the wetting agent of the formula ï4675 3 1 2 1 \ / 2 2 )3 3 in (3:4) isopropanoL/water and O.S ml of water are added, and thewhole is emulsified ultrasonically for S minutes at a power of 100 watt.
2.0 ml of a silver bromide emulsion having a silver content of 6.o g per litre, 0.7 ml of a 1 % aqueous solution of the hardener of the formula ~._N ._ .
\ ~ NH--\ /-~S03Na and 3.8 ml of water are added to 2.5 ml of the emulsion thus obtained, and the mixture is adjusted to a pH value of 6.5 and coated onto subbed, plastic-coated, white paper mounted on a glass plate.
After solidification, the paper is dried at room temperature in a circulating-air oven.
After 3 days, samples cut to 35 x 180 mm are exposed behind a step wedge at 3,000 lux x seconds and then processed by the Kodak Ektaprint 2~Dprocess.
a) One part of the yellow wedges thus obtained is irradiated in an Atlas Weather-O-meter with a 2,500 W xenon lamp behind a W filter (Kodak 2C) with 63 KJoule/cm2 and a second part is irradiated with 168 KJoule/cm (one further comparative sample of each does not contain any light stabiliser).
The table shows the percentage decrease in density, the original 4f~7S
density being 1.0:
With W filter _ _ Light stabiliser Density loss at 440 nm in percent No. (D = 1.0), quantity of light 63 KJ/cm 168 KJ/cm L ~7 ~
b) A part of the yellow wedges obtained is irradiated as described under a~ but without a W filter, with 21 KJoule/cm and a further part is irradiated, likewise without a W filter, with 63 KJoule/cm (one further comparative sample of each does not contain any light stabiliser).
The table shows the percentage decrease in density, the original density being 1.0:
Without W filter Light stabiliser Density loss at 440 nm in percent No. (D - 1.0), quantity of light 21 KJ14Cm2 ¦ 63 KJ/cm .
5 1 15 .
C
~L~3L46~75 Example 3: 0.025 g of the cyan coupler of the formula Cl 2H5 CH -C--CH
~H 3~3 CH3 CO-CH-O--~ o------C--C H
' 2 5 CH3 CH ~-3 Cl and 0.025 g of a light stabiliser from the table which follows are dissolved in 1 ml of a mixture of tricresyl phosphate and ethyl acetate (l.S g in 100 ml). To this solution, 7.0 ml of a 6 Z
gelatine solution, 0.5 ml of an 8 ~ solution of the wetting agent of the formula CH3-C- CH2- C~ --0-(CH2CHz0)3SO3Na ~H3 CH3 in (3:4) isopropanoL/water and 0.5 ml of water are added9 and the whole is emulsified ultrasonically for 5 minutes at a power of 100 watt.
2.0 ml of a sllver bromide emulsion havi.ng a silver content of
C
~L~3L46~75 Example 3: 0.025 g of the cyan coupler of the formula Cl 2H5 CH -C--CH
~H 3~3 CH3 CO-CH-O--~ o------C--C H
' 2 5 CH3 CH ~-3 Cl and 0.025 g of a light stabiliser from the table which follows are dissolved in 1 ml of a mixture of tricresyl phosphate and ethyl acetate (l.S g in 100 ml). To this solution, 7.0 ml of a 6 Z
gelatine solution, 0.5 ml of an 8 ~ solution of the wetting agent of the formula CH3-C- CH2- C~ --0-(CH2CHz0)3SO3Na ~H3 CH3 in (3:4) isopropanoL/water and 0.5 ml of water are added9 and the whole is emulsified ultrasonically for 5 minutes at a power of 100 watt.
2.0 ml of a sllver bromide emulsion havi.ng a silver content of
6.0 g per litre, 0.7 ml of a 1 % aqueous solution of the hartener of the formula C~, ~\ ~'-NH--\ ~-~S03Na ~1467~
- 30 ~
and ~.8 ml of water are added to 2.5 ml of the emulsion thus obtained, and the mixture is adjusted to a pH value of 6.5 and coated onto subbed, plastic-coated, white paper mounted on a glass plate.
After solidification, the paper is dried at room temperature in a circulating-air oven.
Analogously to the procedure described in Example 2a and b, layers are prepared, exposed and processed.
The wedges obtained are stored in an air-conditioned cabinet at 60C and 70~ relative humidity.The table which follows shows the percentage decrease in the cyan density, the original density being 1.0 in the red (measured by means of a Densitometer ~ TR 924 Status A, from Messrs Macbeth).
Llght stabiliser Density loss in the red in percent No. (D - 1.0, 60C/70~ relative humidity) _ 14 days 28 days 29 ~ ~ 26 _
- 30 ~
and ~.8 ml of water are added to 2.5 ml of the emulsion thus obtained, and the mixture is adjusted to a pH value of 6.5 and coated onto subbed, plastic-coated, white paper mounted on a glass plate.
After solidification, the paper is dried at room temperature in a circulating-air oven.
Analogously to the procedure described in Example 2a and b, layers are prepared, exposed and processed.
The wedges obtained are stored in an air-conditioned cabinet at 60C and 70~ relative humidity.The table which follows shows the percentage decrease in the cyan density, the original density being 1.0 in the red (measured by means of a Densitometer ~ TR 924 Status A, from Messrs Macbeth).
Llght stabiliser Density loss in the red in percent No. (D - 1.0, 60C/70~ relative humidity) _ 14 days 28 days 29 ~ ~ 26 _
Claims (12)
1. A colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an interlayer and/or a protective layer, contains at least one polyalkylpiperidine compound as a light stabiliser, wherein the polyalkylpiperidine compound is of the formula I
(I) in which R1 and R3 independently of one another are hydrogen or methyl, R2 is hydroxyl, Cl-C12-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, 2-hydroxyethyl, C2-C11-alkoxyalkyl, C7-C14-aralkyl or a group of the formula -(CH2)p -CH(R6)-X1 or -CH(R6)-X2, in which p is one of the numbers l, 2 or 3, X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)OR7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, Cl-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R8 being hydrogen or Cl-C4-alkyl, or R7 and R8, together with the nitrogen atom to which they are bonded, forming a 5-membered or 6-membered heterocyclic ring, or R2 is a group of the formula II
L-CO- (II) in which L is hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C3-C4-alkynyl, C3-C12-cycloalkyl, C7-Cl4-alkaryl, C7-C14-aralkyl, chloromethyl, unsubstituted phenyl, phenyl which is substituted by two Cl-C4-alkyls and one hydroxyl, or a group -OR9 in which R9 is Cl-C12-alkyl, cyclohexyl, C2-Cl2-alkenyl, benzyl or phenyl, or L is a group of the formula III
(III) or R2 is a group of the formula IV
(IV) in which R10 and R11 independently of one another are Cl-C12-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R11 additionally can also be hydrogen, or R2 is a group of the formula V
(V) in which A' is methylene or a group -CH2-CH(R13)- and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenyl, or R2 is a group of the formula VI
(VI) in which B is a group C H2r, in which r is a number from 2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, phenylene, xylylene, bitolylene, C5-C12-cycloalkylene or a group -CONH-B1-NHCO-, in which B1 is a group CrH2r, phenylene, naphtylene, tolylene or a group of the formulae in which R' is hydrogen, methyl or ethyl, R" is hydrogen or methyl and r is as defined above, or R2 is one of the groups -S(O) R14 or -OR15, in which z is the number 1 or 2, R14 is Cl-C12-alkyl, C7-Cl4-alkaryl or phenyl and R15 is Cl-Cl2-alkyl, C3-C12-alkenyl, C7-C14-aralkyl or a group of the formula L'-C0-, in which L' is as defined above for L, R4 and R5 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, C7-C14-aralkyl, C7-C14 alkaryl or phenyl and R4 can additionally also be hydrogen or a group of the formula Ia (Ia) in which R1, R2, R3, R5, A, Y, m and n are as defined and M is a direct bond, , -CH2-S-CH2-, -CH2-0-CH2-, -O- and -N(D3)-, and D1 and D2 independently of one another are hydrogen, Cl-C18-alkyl, alkyl interrupted by 1 to 3 -S- or phenyl, or D1 and D2, together with the C atom linking them, form a 5-membered or 6- membered aliphatic ring and D3 is hydrogen, C1-C18-alkyl or phenyl, Y is -O-, n and m independently of one another are zero or 1, and A is methylene or a group -CH(R20)- or -CH2-C(E)(G)-, in which R20 is hydrogen, methyl, ethyl, phenoxymethyl or phenyl, E is cyano or a group -C(O)OR21, -C(O)R22, -SO2R22, -P(O)(OR23) , -C(O)NR24R25 or -CHO, in which R21 is C1-C4-alkyl R22 is Cl-C12-alkyl, C7-C14-alkaryl or phenyl, R23is Cl-C18-alkyl, phenyl or allyl, and R24 and R25 independently of one another are hydrogen, Cl-C18-alkyl or phenyl, and G is hydrogen, Cl-C18-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-C18-alkylcyclo-alkyl, C6-C14-cycloalkylalkyl, C7-C14-aralkyl, C7-Clg-alkyl-aralkyl, phenyl, or Cl-C18-alkyl which is substituted by phenoxy, C7-C10-alkylphenoxy, benzyloxy, cyclohexyloxy, cyano, -COOR26, -OCOR27 or -P(O)(OR28)2, R26 being C1-C18-alkyl, C3-C12-cycloalkyl or a group of the formula VII
(VII) R27 being Cl-C18-alkyl, C3-C12-cycloalkyl, phenyl, C7-C14-aralkyl or a group of the formula III and R28 being Cl-C18-alkyl, allyl or phenyl, or G is C2-C18-alkyl interrupted by -O-, -S-, -SO- or -SO2-, a group of the formula VII or a group of the formula in which R29 and R30 independently of one another are C1-C4-alkyl and R30 additionally can also be hydrogen, or if E is a group -C(O)R22, G and R22 together are trimethylene or tetramethylene.
(I) in which R1 and R3 independently of one another are hydrogen or methyl, R2 is hydroxyl, Cl-C12-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, 2-hydroxyethyl, C2-C11-alkoxyalkyl, C7-C14-aralkyl or a group of the formula -(CH2)p -CH(R6)-X1 or -CH(R6)-X2, in which p is one of the numbers l, 2 or 3, X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)OR7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, Cl-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R8 being hydrogen or Cl-C4-alkyl, or R7 and R8, together with the nitrogen atom to which they are bonded, forming a 5-membered or 6-membered heterocyclic ring, or R2 is a group of the formula II
L-CO- (II) in which L is hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C3-C4-alkynyl, C3-C12-cycloalkyl, C7-Cl4-alkaryl, C7-C14-aralkyl, chloromethyl, unsubstituted phenyl, phenyl which is substituted by two Cl-C4-alkyls and one hydroxyl, or a group -OR9 in which R9 is Cl-C12-alkyl, cyclohexyl, C2-Cl2-alkenyl, benzyl or phenyl, or L is a group of the formula III
(III) or R2 is a group of the formula IV
(IV) in which R10 and R11 independently of one another are Cl-C12-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R11 additionally can also be hydrogen, or R2 is a group of the formula V
(V) in which A' is methylene or a group -CH2-CH(R13)- and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenyl, or R2 is a group of the formula VI
(VI) in which B is a group C H2r, in which r is a number from 2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, phenylene, xylylene, bitolylene, C5-C12-cycloalkylene or a group -CONH-B1-NHCO-, in which B1 is a group CrH2r, phenylene, naphtylene, tolylene or a group of the formulae in which R' is hydrogen, methyl or ethyl, R" is hydrogen or methyl and r is as defined above, or R2 is one of the groups -S(O) R14 or -OR15, in which z is the number 1 or 2, R14 is Cl-C12-alkyl, C7-Cl4-alkaryl or phenyl and R15 is Cl-Cl2-alkyl, C3-C12-alkenyl, C7-C14-aralkyl or a group of the formula L'-C0-, in which L' is as defined above for L, R4 and R5 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, C7-C14-aralkyl, C7-C14 alkaryl or phenyl and R4 can additionally also be hydrogen or a group of the formula Ia (Ia) in which R1, R2, R3, R5, A, Y, m and n are as defined and M is a direct bond, , -CH2-S-CH2-, -CH2-0-CH2-, -O- and -N(D3)-, and D1 and D2 independently of one another are hydrogen, Cl-C18-alkyl, alkyl interrupted by 1 to 3 -S- or phenyl, or D1 and D2, together with the C atom linking them, form a 5-membered or 6- membered aliphatic ring and D3 is hydrogen, C1-C18-alkyl or phenyl, Y is -O-, n and m independently of one another are zero or 1, and A is methylene or a group -CH(R20)- or -CH2-C(E)(G)-, in which R20 is hydrogen, methyl, ethyl, phenoxymethyl or phenyl, E is cyano or a group -C(O)OR21, -C(O)R22, -SO2R22, -P(O)(OR23) , -C(O)NR24R25 or -CHO, in which R21 is C1-C4-alkyl R22 is Cl-C12-alkyl, C7-C14-alkaryl or phenyl, R23is Cl-C18-alkyl, phenyl or allyl, and R24 and R25 independently of one another are hydrogen, Cl-C18-alkyl or phenyl, and G is hydrogen, Cl-C18-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-C18-alkylcyclo-alkyl, C6-C14-cycloalkylalkyl, C7-C14-aralkyl, C7-Clg-alkyl-aralkyl, phenyl, or Cl-C18-alkyl which is substituted by phenoxy, C7-C10-alkylphenoxy, benzyloxy, cyclohexyloxy, cyano, -COOR26, -OCOR27 or -P(O)(OR28)2, R26 being C1-C18-alkyl, C3-C12-cycloalkyl or a group of the formula VII
(VII) R27 being Cl-C18-alkyl, C3-C12-cycloalkyl, phenyl, C7-C14-aralkyl or a group of the formula III and R28 being Cl-C18-alkyl, allyl or phenyl, or G is C2-C18-alkyl interrupted by -O-, -S-, -SO- or -SO2-, a group of the formula VII or a group of the formula in which R29 and R30 independently of one another are C1-C4-alkyl and R30 additionally can also be hydrogen, or if E is a group -C(O)R22, G and R22 together are trimethylene or tetramethylene.
2. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkyl-piperidine compound of the formula X
(X) in which R1 is hydrogen or methyl, R4 and R5 independently of one another are Cl-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Xa (Xa) in which M is a direct bond, -CH(D2)- or -S- and D2 is hydrogen or C1-C8-alkyl, A is methylene, ethylene or a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen, C1-C18-alkyl, allyl, cyclohexyl, benzyl or one of the two groups of the formulae in which R30 is methyl or tert.-butyl, or E and G together form a group -CO-(CH2)4-, n and m are as defined in claim 1, R2 is hydroxyl, Cl-C4-alkyl, allyl, methallyl, propargyl, benzyl, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of the formula -(CH2)p-CH(R6)-Xl or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3, X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)R7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl R7 being hydrogen, C1-C8-alkyl, vinyl, allyl, methallyl, C5-C8-cycloalkyl, phenyl or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, C1-C4-alkyl, vinyl, allyl, cyclohexyl, phenyl, benzyl, chloromethyl or a group -OR9, in which R9 is Cl-C8-alkyl,cyclohexyl, vinyl, allyl or methallyl, or L is a group of the formula III, in which m, A, R4 and R5 are as defined in this claim, and R3 is hydrogen, or R2 is a group of the formula IV, in which R10 and R11 independently of one another are Cl-C12-alkyl, cyclohexyl or phenyl and R11 additionally can also be hydrogen, or R2 is a group of the formula XI
(XI) in which n, R4, R5 and Y are as defined in this claim, A' is methylene or a group -CH2-CH(R13)-, q is zero or 1, and R12 and R13 independent-ly of one another are hydrogen or methyl, or R2 is a group of the formula XII
(XII) in which A, R4, R5, Y, n and m are as defined in this claim and B is a group ?CH2?r or -CONH(CH2??NHCO-, in which r is one of the numbers Z to 8, or C4-C8-alkenylene, xylylene or bitolylene, or R2 is one of the groups -SO2R14 or -OR15, in which R14 is Cl-C4-alkyl, p-tolyl or phenyl and R15 is Cl-C4-alkyl, benzyl or a group of the formula L'-CO-, in which L' is as already defined for L in this claim, and Y is -O-.
(X) in which R1 is hydrogen or methyl, R4 and R5 independently of one another are Cl-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Xa (Xa) in which M is a direct bond, -CH(D2)- or -S- and D2 is hydrogen or C1-C8-alkyl, A is methylene, ethylene or a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen, C1-C18-alkyl, allyl, cyclohexyl, benzyl or one of the two groups of the formulae in which R30 is methyl or tert.-butyl, or E and G together form a group -CO-(CH2)4-, n and m are as defined in claim 1, R2 is hydroxyl, Cl-C4-alkyl, allyl, methallyl, propargyl, benzyl, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of the formula -(CH2)p-CH(R6)-Xl or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3, X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)R7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl R7 being hydrogen, C1-C8-alkyl, vinyl, allyl, methallyl, C5-C8-cycloalkyl, phenyl or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, C1-C4-alkyl, vinyl, allyl, cyclohexyl, phenyl, benzyl, chloromethyl or a group -OR9, in which R9 is Cl-C8-alkyl,cyclohexyl, vinyl, allyl or methallyl, or L is a group of the formula III, in which m, A, R4 and R5 are as defined in this claim, and R3 is hydrogen, or R2 is a group of the formula IV, in which R10 and R11 independently of one another are Cl-C12-alkyl, cyclohexyl or phenyl and R11 additionally can also be hydrogen, or R2 is a group of the formula XI
(XI) in which n, R4, R5 and Y are as defined in this claim, A' is methylene or a group -CH2-CH(R13)-, q is zero or 1, and R12 and R13 independent-ly of one another are hydrogen or methyl, or R2 is a group of the formula XII
(XII) in which A, R4, R5, Y, n and m are as defined in this claim and B is a group ?CH2?r or -CONH(CH2??NHCO-, in which r is one of the numbers Z to 8, or C4-C8-alkenylene, xylylene or bitolylene, or R2 is one of the groups -SO2R14 or -OR15, in which R14 is Cl-C4-alkyl, p-tolyl or phenyl and R15 is Cl-C4-alkyl, benzyl or a group of the formula L'-CO-, in which L' is as already defined for L in this claim, and Y is -O-.
3. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkyl-piperidine compound of the formula XIV
(XIV) in which m is zero or 1, A is methylene or ethylene, R4 and R5 independently of one another are methyl or tert.-butyl, Y is -O-, and R2 is hydroxyl, methyl, allyl, benzyl, 2-hydroxyethyl, acetyl, acryloyl, methoxy, acetoxy or a group of the formula XV
(XV) in which m, A, R4 and R5 are as defined in this claim, or is a group of the formula IV, in which R10 is Cl-C8-alkyl, cyclohexyl or phenyl and R11 is hydrogen, Cl-C8-alkyl or cyclohexyl.
(XIV) in which m is zero or 1, A is methylene or ethylene, R4 and R5 independently of one another are methyl or tert.-butyl, Y is -O-, and R2 is hydroxyl, methyl, allyl, benzyl, 2-hydroxyethyl, acetyl, acryloyl, methoxy, acetoxy or a group of the formula XV
(XV) in which m, A, R4 and R5 are as defined in this claim, or is a group of the formula IV, in which R10 is Cl-C8-alkyl, cyclohexyl or phenyl and R11 is hydrogen, Cl-C8-alkyl or cyclohexyl.
4. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkyl-piperidine compound of the formula XIV
(XIV) in which R2 is a group of the formula and m, R4, R5 and Y are as defined in claim 3.
(XIV) in which R2 is a group of the formula and m, R4, R5 and Y are as defined in claim 3.
S. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkyl-piperidine compound of the formula XIV
(XIV) in which A is a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen or one of the two groups of the formulae or E and G together form a group -CO-?CH2)4-, R2 is -CHO, acetyl or acryloyl and m, R4, R5 and Y are as defined in claim 3.
(XIV) in which A is a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen or one of the two groups of the formulae or E and G together form a group -CO-?CH2)4-, R2 is -CHO, acetyl or acryloyl and m, R4, R5 and Y are as defined in claim 3.
6. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combination with a cyan coupler, magenta coupler and yellow coupler.
7. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combination with an ultraviolet absorber.
8. A colour-photographic recording material according to claim 7, wherein the ultraviolet absorber is a compound of the benzophenone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole or imidazole type.
9. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combination with a cyan coupler, magenta coupler and yellow coupler and with a UV absorber in the same layer.
10. A colour-photographic recording material according to claim 1, which contains 1 to 2,000 mg of the light stabiliser per m2 of the layer into which the latter is incorporated.
11. A process for the production of photographic colour images by imagewise exposure and colour development of a colour-photo-graphic recording material according to claim 1.
12. A photographic colour image obtained by the process according to claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000499753A CA1229610A (en) | 1981-12-17 | 1986-01-16 | Colour-photographic recording material |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH8067/81-7 | 1981-12-17 | ||
| CH806781 | 1981-12-17 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000499753A Division CA1229610A (en) | 1981-12-17 | 1986-01-16 | Colour-photographic recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1214675A true CA1214675A (en) | 1986-12-02 |
Family
ID=4334624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000417792A Expired CA1214675A (en) | 1981-12-17 | 1982-12-15 | Colour-photographic recording material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4452884A (en) |
| EP (1) | EP0082817B1 (en) |
| JP (1) | JPS58114036A (en) |
| CA (1) | CA1214675A (en) |
| DE (1) | DE3275592D1 (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3375431D1 (en) * | 1982-11-18 | 1988-02-25 | Ciba Geigy Ag | Colour-photographic recording material |
| DE3375432D1 (en) * | 1982-11-26 | 1988-02-25 | Ciba Geigy Ag | Colour-photographic recording material |
| EP0111447B1 (en) * | 1982-12-03 | 1988-01-07 | Ciba-Geigy Ag | Colour-photographic recording material |
| DE3375332D1 (en) * | 1982-12-08 | 1988-02-18 | Ciba Geigy Ag | Colour-photographic recording material |
| DE3377596D1 (en) * | 1982-12-16 | 1988-09-08 | Ciba Geigy Ag | Colour-photographic recording material |
| DE3375231D1 (en) * | 1982-12-16 | 1988-02-11 | Ciba Geigy Ag | Colour-photographic recording material |
| US5096949A (en) * | 1983-11-07 | 1992-03-17 | The B. F. Goodrich Company | N,N-disubstituted, α-(3,5-dialkyl-4-hydroxyphenyl)-α,α-disubstituted acetamides and composition stabilized therewith |
| US4920228A (en) * | 1983-11-07 | 1990-04-24 | The B. F. Goodrich Company | N,N-disubstituted, α-(3,5-dialkyl-4-hydroxyphenyl)-α,α-disubstituted acetamides and composition stabilized therewith |
| JPS60232550A (en) | 1984-05-02 | 1985-11-19 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material |
| JPS62161150A (en) * | 1986-01-08 | 1987-07-17 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| US4797350A (en) * | 1986-04-16 | 1989-01-10 | Konishiroku Photo Industry Co., Ltd. | Process for forming dye-image using a developer comprising an image stabilizer, a hydroxylamine and not containing benzyl alcohol |
| ATE82962T1 (en) * | 1986-07-16 | 1992-12-15 | Goodrich Co B F | N-(SUBSTITUTED-CYCLIC-ALKYLENIMINE)-ALPHA (3,5-DIALKYL-4-HYDROXYPHENYL)-ALPHA, ALPHADIALKYLACETAMIDES. |
| EP0256537B1 (en) | 1986-08-15 | 1992-12-30 | Fuji Photo Film Co., Ltd. | Color print and a method for producing the same |
| DE3641014A1 (en) * | 1986-12-19 | 1988-06-16 | Wolfen Filmfab Veb | PHOTOPOLYMERIZABLE MATERIAL |
| DE3887428D1 (en) * | 1987-09-30 | 1994-03-10 | Ciba Geigy | Phenolic thiane derivatives. |
| DE3871062D1 (en) * | 1987-09-30 | 1992-06-17 | Ciba Geigy Ag | STABILIZERS FOR COLOR PHOTOGRAPHIC RECORDING MATERIALS. |
| US5149828A (en) * | 1987-09-30 | 1992-09-22 | Ciba-Geigy Ag | Stabilizers for color photography recording materials |
| EP0323803A1 (en) * | 1987-12-30 | 1989-07-12 | Ciba-Geigy Ag | Stabilization of coatings by N-formylated hindered amines |
| US4859759A (en) * | 1988-04-14 | 1989-08-22 | Kimberly-Clark Corporation | Siloxane containing benzotriazolyl/tetraalkylpiperidyl substituent |
| JPH02217845A (en) * | 1989-02-20 | 1990-08-30 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JP3289786B2 (en) * | 1992-08-27 | 2002-06-10 | パイオニア株式会社 | Information recording medium |
| JP3333252B2 (en) * | 1992-12-24 | 2002-10-15 | 住化バイエルウレタン株式会社 | Method for preventing coloration of diphenylmethane diisocyanate compound |
| GB2279649B (en) * | 1993-07-08 | 1997-07-16 | Ciba Geigy Ag | Phenolic s-triazines |
| DE19648723B4 (en) * | 1995-11-27 | 2005-03-10 | Ciba Sc Holding Ag | 4-aminophenol derivatives |
| JP3584119B2 (en) | 1996-04-05 | 2004-11-04 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| JPH11125889A (en) * | 1997-08-22 | 1999-05-11 | Fuji Photo Film Co Ltd | Method for enhancing light-fastness of image and image forming material |
| US7234686B2 (en) * | 1997-12-03 | 2007-06-26 | Peter Stone | Fail-safe cleat with automatic in-line locking cam and quick-release slot |
| US7073780B2 (en) * | 1997-12-03 | 2006-07-11 | Peter Stone | Fail-safe cleat with automatic in-line locking cam |
| US20040201005A1 (en) * | 1997-12-03 | 2004-10-14 | Peter Stone | Fail-safe device for raising/lowering articles |
| WO2006022405A1 (en) | 2004-08-24 | 2006-03-02 | Fujifilm Corporation | Silver halide color photographic photosensitive material and method of image forming |
| WO2008123504A1 (en) | 2007-03-30 | 2008-10-16 | Fujifilm Corporation | Ultraviolet ray absorber composition |
| JP5244437B2 (en) | 2008-03-31 | 2013-07-24 | 富士フイルム株式会社 | UV absorber composition |
| JP2009270062A (en) | 2008-05-09 | 2009-11-19 | Fujifilm Corp | Ultraviolet absorbent composition |
| JP2010059235A (en) | 2008-09-01 | 2010-03-18 | Fujifilm Corp | Ultraviolet absorbent composition |
| JP5261319B2 (en) | 2008-09-10 | 2013-08-14 | 富士フイルム株式会社 | Lighting cover |
| KR20160082814A (en) * | 2014-12-29 | 2016-07-11 | 삼성디스플레이 주식회사 | Luquid crystal stabilizer, luquid crystal composition comprising the same and liquid crystal display device comprising the same |
| CN105199142A (en) * | 2015-10-28 | 2015-12-30 | 江苏极易新材料有限公司 | Stabilizer with two polymer and grease ageing delaying function group structures, and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596926A (en) * | 1949-12-16 | 1952-05-13 | Gen Aniline & Film Corp | Preparation of azine dye images |
| US3183219A (en) * | 1963-10-29 | 1965-05-11 | Polaroid Corp | 2-benzoyl-5-methoxyphenyl acrylate and polymers thereof |
| GB1395159A (en) * | 1971-11-30 | 1975-05-21 | Ciba Geigy Ag | Tetra-hydropyridine derivatives |
| DE2656769A1 (en) * | 1975-12-29 | 1977-07-14 | Ciba Geigy Ag | NEW PHENOL STABILIZERS |
| EP0011051B1 (en) * | 1978-11-06 | 1982-09-15 | Ciba-Geigy Ag | Colour-photographic recording material, process for its stabilisation and production of colour-photographic images |
-
1982
- 1982-12-13 DE DE8282810538T patent/DE3275592D1/en not_active Expired
- 1982-12-13 EP EP82810538A patent/EP0082817B1/en not_active Expired
- 1982-12-15 CA CA000417792A patent/CA1214675A/en not_active Expired
- 1982-12-17 US US06/450,513 patent/US4452884A/en not_active Expired - Lifetime
- 1982-12-17 JP JP57221738A patent/JPS58114036A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58114036A (en) | 1983-07-07 |
| EP0082817A1 (en) | 1983-06-29 |
| DE3275592D1 (en) | 1987-04-09 |
| JPH0340373B2 (en) | 1991-06-18 |
| US4452884A (en) | 1984-06-05 |
| EP0082817B1 (en) | 1987-03-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |